Process and apparatus for producing printing ink



June l2. i928,

4. .J. JAKQSKY PROCESS AND APPARATUS FOR PRODUCING PRINTING INK FiledNov. 1, 1926 A TTORNEY; e

June 12, 1928. w'isgms J. J. JAKOSKY' PROCESS AND APPARATUS FORPKRIODUCING PRINTING INK lJune 12, 192s. 1,673,245

J. J. JAKOSKY PROCESS AND APPARATUS FOR PRODUCING PRINTING INK ATTORNES.

June 12, 1928.

1,673,245 J. J. JAKOSKY l PROCESS AND APPARATUS FOR BRODUCING PRINTINGINK Filed Now/.1, 1926 5-Sheets'-Sheet 4 June 12, 192s. r 'i 1,673,245

J. J. JAKQS-KY PROCESS AND APPARATUS FOR PRODUGING PRINTING INK FiledNoi/.1, 1926 s sheeJf.,s-sheetl 5 ffg Y Patented June 12, i928.

if ica,

JOHN J. JAKOSKY, OF LOSANGELES, CALIFORNIA.

PROCESS AND APPARATUS FOR PRODUCING PRINTING INK.

Application `il'ed November 1, 1926. Serial No. 145,575.

This invention relates to the production of printing inks consisting ofcarbon black suspended in a suitable liquid hydrocarbon or othercarbon-bearing oil, and the main object of the invention is to producean ink of this type as simply and as cheaply as possible. The termcarbon-bearing oil is used herein as meaning an oil whose majorconstituents contain carbon as a part of their chemical composition.

A particular object of the invention is to provide for the directproduction of such ink, as distinguished from present methods of firstproducing a dry, substantially oil- -free-carbon black'and then mixingthe same with the oil which is to be used as a vehicle.

The process which I have devised for this purpose consists essentially,in its preferred embodiment, in heating a hydrocarbon or othercarbon-bearing oil which is suitable for use as a vehicle for ink, tosuch a temperature and under such conditions as to cause rapid, andpractically instantaneous, dissociation of a portion of such oil intocarbon in the form of carbon black, and hydrogen or other gas;withdrawing the gas as formed, from the oil; and continuing or repeatingsuch treatment until the resulting carbon is present in the oil or in aportion thereof substantially in the proportion required for printingink, so as toV produce a `product which may be marketed directly asprinting ink. The heating of the oil is preferably accomplished by meansof an electric arc, although. other methods of heatingmay be employed,as for example, a high temperature flame such as the Oxy-hydrogenflame.' Furthermore, the heating to the dissociation temperature ispreferably carried out in a localized portion of a body of the oil,whereby a body of oil at a relatively lower temperature is maintainedaround the region of such localized heating or dissociation, and Iprefer to carry out the process in such manner as to cause the productsof dissociation- (carbon and hydrogen or other gas) to be substantiallyimmediately withdrawn orA removed from the dissociation zone into suchbody of relatively lower temv perature oil, so .as to quickly cool thecarbon below the temperature of dissociation and -maintain itsubstantially in the finely divided and unagglomerated condition inwhich it is first formed. One effect of this quick cooling of the carbonis to prevent agglomeration which might otherwise occur and which wouldprevent or seriously interfere with its use as a pigment in printingink. 'Ihe carbon black produced in this manner is extremely finelydivided and has a high tinting strength, and is otherwise well suitedfor use in printing, and the term carbon black as used throughout thisspecification will be understood to mean a carbon black having thesecharacteristics. The preferable use of the electric arc for heating tothe dissociation temperature and the above-described method of coolingthe carbon immediately after formation, have been disclosed and claimedin my United States Patent No. 1,597,277, issued August 24, 1926. Thepresent invention contemplates the application of such methods ofdissociation and cooling in a novel process for the direct production ofprinting ink from oil. l

More specifically, the method used according to the present inventionincludes maintaining a body of a suitable oil at a relatively lowtemperature; setting up a heating or dissociation zone of the requiredtemperature at a localized position in said body of oil; causingportions of such body of oil to pass through such dissociation zone,resulting in formation of carbon black which is immediately disseminatedinto lthe sur'- rounding body of oil and of hydrogen or other gas whichalso passes off through the oil; repeating such passage of the oilthrough the dissociation zone or passing it through a seconddissociation zone (with or without settling or other thickening actionbetween successive passages) until the oil,

or a certain settled or thickened portion thereof, containssubstantially the necessary' proportion of carbon black for use asprint-` ing ink; and then withdrawing, separating, or collecting suchoil or such thickened portion thereof containing such proportion ofcarbon black.

While I have mentioned that the body of oil surrounding the dissociationzone is maintained at a. relatively low temperature as compared to thetemperature of such zone,

4it will be `understood that such relatively low temperature may itselfbe considerably above normal or atmospheric temperature, as it is onlynecessary that it be low enough to cool the carbon black quickly to sucha point .that it will retaln substantially its original characteristics.`In order, therefore, to increase the fluidity of the body of oil, andalso to minimize the amount of heat required in the dissociation zoneto' heat theA 'oil from the surrounding temperature to the dissociationtemperature and hence .increase to a maximum the efficiency ofutilization of the heat in such zone purely for dissoclation purposes, Imay in some cases prefer to maintain the body of oil surrounding thedissociation zo'ne at a temperature above normal temperature and justlow enough to prevent harmful changes in the characteristics of thecarbon black after formation and to also prevent appreciablevaporization of the oil. For this purpose auxiliary heating means may beprovided in the bod of oil, or in the pathv of circulation of suc oil.

Another feature of my invention in. its preferred form, consists inmaintainin both in the dissociation zone and in thebo y of oilsurrounding the same, as low a presdissociation, and hence vtheefficiency of the process., is dependent on the extent of such surfacewhich in turn depends on the size of the arc or the high temperatureflame.

` Therefore, by maintaining a pressure as above described the' maximumliquid surface is'v exposed to the dissociating action and the maximumefficiency is realized.- The use of a pressure as low as possible alsoincreases the rate of dissociation and increases the tendency toformation of hydrogen,.methane, and other gaseous-products.

Such pressure Will of course in most cases be other than atmospheric andmay be either sub-atmospheric or super-atmospheric. For example,.withheavy oils a pressure as low as one-tenth of an l atmosphere (absolutepressure) or less may be employed without causing serious vaporizationthereof from the liquid body surrounding the dissociation zone, whilewith more volatile oils pressures nearer atmospheric pressure, and insome cases even above atmospheric pressure, may

l be employed. In general, however, I prefer to employ a pressure whichis only sli htly above the vapor pressure of the most vo atile Assumingthat this is the case, it is evident that the rate of substantialconstituent of the oil at the temperature maintained in the body of oilsui'- rounding lthe dissociation zone.

One modification of the invention conists in the production of highergrade inks for special purposes b first producing a base in accordancewit above, such base consisting of carbon black produced by dissociationof; and suspended in, a relatively cheap oil, such as a hydrocarbon oil,and then adding thereto additional oils, dryers, or varnishes, as may benecessary to produce such higher grade ink.

Another step Which may be incorporated in the process is that o fsubjecting the suspension of carbon' black in the oil from which it Wasformed to a grinding operation to grind any lumps or large particles offoreign matter which might be. deleterious to the use of such materialas printing ink, or to a separating operation to remove hard particlesor grit, or to both such grinding and separating operations.

rIhe carbon-bearing oil which is used in the present process must ofcourse be an oil which is capable of holding carbon black in suspensionin a linely divided state and which possesses suchpropertes of fluidity,

viscosity, volatility, and the like as to render it suitable as avehicle for printing ink. In some cases, however, when it is .desired touse a heavy oil as a vehicle 1n the ink,

lit may be found advantageous, in order to increase the iuidity of suchoil during its passage through the dissociation zone and other parts ofthe apparatus, and possibly also in order to increase the production ofcarbon black, to mix a lighter oil, such as kerosene or the like,4w'ithsuch heavier oil, o1; to employ a mixture of such `oils, subjecting themixture to dissociation as above described to form a suspension ofcarbon black therein, and then subjecting the material to distillationso as to remove the lighter oil or a portion thereof, and produce an inkcomprising any oil of the desired characteristics with the yproper p-roportion of carbon black therein. When car- .rying out the process inthis manner the lighter fractions distilled oil' are preferably mixedwith a further quantity of heavy oil and returned tothe treater. Arelatively the methods outlined small quantity of light oil would thusbe p required, asit could be used over and over again in the process,except for such portion as is decomposed or left in the finished ink.

The invention also comprises certain special apparatus, as hereinafterdescribed,

which is particularly advantageous for car-` rying out some of theprocesses or operations above mentioned.

The accompanying drawings illustrate certain forms of apparatusaccording to my invention and referring thereto: v

Fig. Yl-is a diagrammatic side elevation of one form of apparatus forcarrying out the complete process.

Fig. 2 is a similar View oa modified form of such apparatus.

Fig. 3 is a vertical section of one form of reaction chamber foreffectingdissociation ot' the oil. A

Fig. 4 is a diagrammatic plan view ot the driving means for rotating theelectrodes shown in Fig. 3.

Fig. 5 i-s a horizontal section on line 5-5 in Fig. 3.

Fig. (i is a vertical section of another form of reaction chamber.

Fig. 7 is ahorizontal section on line 7-7 in Fig. (i.

Fig. S is a vertical section ot' another type oi' reaction chamber.

Fig. 9 is a horizontal section on line 9--9 in Fig. S.

Fig. 10 is a vertical section otanother type ot' reaction chamber.

Fig. 11 is a horizontal section on line 11-11 in Fig. 10.

Figs. 12 and 13 are diagrammatic side elevations showing furthermodiicat'ons of the complete apparatus.

Fig. 14 is a diagrammatic side elevation of another modification of acomplete apparatus.

The apparatus shown in Fig. 1 is adapted for carrying out thedissociation of the oil under a conditon of partial vacuum orsubatmospheric pressure. Such apparatus comprises an oil supply chamber1, a scrub.- ber 2, a reaction vessel or chamber 3, and a storageorsettling chamber 4 for the finished ink. A supply pipe 5 provided withvalve G leads to supply chamber 1 for sup plying thereto the oil to beused in the process.. Pipe 8 provided with regulating valve 9 leads fromchamber 1 to scrubber A2, said scrubber being adapted to permit downwardpassage of oil therethrough in such manner as to exert a scrubbingaction on the vapors passing upwardly therethrough as hereinafterdescribed. For this purpose said -scrubber may be provided With aplurality of horizontal trays 11 disposed one above the other, each ofsaid trays being adapted to maintain a small body or layer of oilthereon and to permit continual overow of such oil therefrom onto thenext lower tray in Well-known manner. The pipe 8 is adapted todischurgeoil into the scrubber above the uppermost of these trays. Anyother suitable type of scrubber may, however, be employed. A pipe 12lead-s from the bottom of scrubber 2 to the reaction vessel 3 so as toconduct oil from the scrubber to the reaction vessel and also conductvapors or gases from the reaction vessel to the scrubber. Agasconducting pipe 13 provided with control valve 14 leads from the topof scrubber 2 to the intake of exhausting -fan or vacuum pump 16,

whence outlet pipe 17 leads the gases away A system of equalizing'pipes23, 24, and

25 may be provided, communicating with one another and alsocommunicating respectively Wit-h supply chamber 1, pipe 13, and storagechamber 4, so as to maintain equal conditions of pressure in all partsof the system. A vacuum gage 26 may be provided at any suitable pointfor indicating the vacuum maintained Within the system, said gage beingconnected, for example to pipe 13 as shown,

The apparatus shown in Fig. 2 is similar to that shown in Fig. 1 but isadapted for carrying out the process at a pressure equal to, or greaterthan, atmospheric pressure. Said apparatus comprises as before oilsupply chamber 1, scrubber 2, reaction chamber 3, ink storagechamber 4,pipes 5, 8, 13, 18, 21, 23, and 25, and valves 6, 9, 14, 19 and 22. Inthis case I have shown as a further modification the inclusion of apre-heater 28 in the pipe line 29 leading from the scrubber to thereaction chamber, said pre-heater boing provided With any suitable meansfor heating the oil passing therethrough, such as a heating coil 30provided With pipes 31 and 32 for circulating a suitable heating mediumsuch as steam therethrough. In this ease a separate pipe 33 is providedfor conducting the vapors and gases from the reaction chamber tothescrubber. With this form of apparatus the system may be maintained underany desired pressure equal to, or greater than atmospheric, suchpressure being created by the formation of hydrogen and other gases fromthe oil and being con trolled by setting valve 14 so as to control therelease of such vapors. The oil may be introduced through pipe 5 under apressure equal to that prevailing Within the System. A pressure gage 34may be connected at any suitable point for indicating the pressureWithin the system.

One form of reaction chamber for effecting dissociation of the oil isillustrated in Figs. -3 to 5, and comprises a cylindrical vessel 36having a conical bottom 37. Said vessel may be covered with suitableheat insulating material indicated at 20. Pipe 12 (or 33) enters the topof said vessel and projects downwardly a short distance into the vesselso as to maintain a vapor space 38 to prevent bumping. A manometer tube39 may level therein an l preferabl A be connected to pipe l2an'd tosaid vapor space so as to indicate by the difference in tendenc of theoil. in ves'- sel 36 to rise a ove the ottom of pipe 12. Suitable meanssuch as electric heating coil 40 maybe provided for heating the mainbody of oil in the vessel 36 to a temperature` above atmospheric butinsuicient to produce appreciable vaporization of any constituents ofthe oil. The lead-in wires 41 and 42 for saidheating coil may passthrough suitable air tight insulating bushings 43. A thermometer well 44may extend into the body of oil and ma be filled with mercury or othersuitable liquid in which a thermometer 45 may be inserted for indicatingthe temperature of the main body of oil.

A pair of rotating electrodes 46 formed of carbon are mounted atythelower en s of shafts 47, which are rotatably mounted ininsulating-bushings 48 extending throu h a cover plate 49 at the top ofvessel 36. uitable packing means 50 are rovided at the upper ends ofinsulatingbus in s 48, so as to provide a substantially air tig t fitaround shafts 47. Said shafts are preferably mounted so as to beinclined ltoward each other at their lower ends and may be provided withadjusting collars 51 by" means of which they may be raised or lowered soas to vary the gap between electrodes 46. Suitable means are providedfor rotating electrodes 46 lin reverse directions, such meanscomprising, 'for example, an endless belt 52 extending over pulleys 53on shafts 47 and over a drive pulley 54 on drive shaft 55 and also overan idler pulley 56 as shown in Figs. 3 and 4. Each of the shafts 47 maybe provided with a contact ring 57, and suitable brushes 58 engage saidcontact rings and are connected by wires 59 to the second'- ary windingof step-up transformer 60 whose primary winding is connected by wires 61to any suitable source of alternatin current. The secondary voltage oftransormer 60 may be any voltage suitable for use in the dissociation ofoil to form carbon black according to my invention and may, for example,be from 10,000 volts or less to 100,000 volts or more. l

The dissociation of the oil is carried out n the above describedreaction vessel as folows:

The oil to be treated enters said' reaction vessel through pipe 12 (or29) and a body of such oil is'maintained within thereaction vessel asindicated at 63. Electrodes 46 are sociation zone yof high tem erature.The arc 1s drawn out untll it`s reslstance becomes s0 high that thevoltage employed is no longer able to maintain the arc, when the arc isextinguished and a new arc is immediately established at the initialposition in t-he gap between adjacent edges of the electrodes. It

is thus seen that `a comparatively restricted l hightemperaturedissociation zone is provided, surrounded by a relativelylarge body nsA of oil at a materially lower temperature than suchdissociation zone.

The high temperature in the dissociation zone causes the oil immediatelysurrounding such zone to be dissociated mainly into car- `bon andhydrogen (together with small amounts of methane and light unsaturatedgases). Due to the rotation of the electrodes a fresh supply lof oil iscontinually drawn into the dissociation zone and the products ofdissociation are disseminated substantially immediately upon theirformation into the surrounding body of relatively low temperature oil.This movement of fresh oil toward the dissociation zone and of thereaction products out of the dissociation zone is also assisted by theconvection currents produced in the body of oil due to heating the oilaround the dissociation zone and by the agitation of the loil due to theescape of hydrogen and other gases upwardly therethrough from thedissociation zone. l The temperature in the dissociation zone itself isrelatively high, for example` from approximately 2000 to 3000 F. whilethe temperature of the oil immediately surrounding such zone ismuchlower than this, as substantially the same temperature prevailsthroughout the entire body of oil outside the dissociation zone due tothe continual agitation and circulation of such oil. A steep temperaturegradient is thus provided between the oil and the arc and the actualdissociation of thev oil into carbon and hydrogen therefore takes placeonly at the surface ofthe oil around the arc or throughout a very thinlayer immediately surrounding the arc. In order therefore to increasethe eiciency of production of carbon black for a given consumption ofelectrical energy it is advantageous to provide an arc having themaximum surface area for a given volume. This object is accomplished inthe above apparat-us by drawing the are out in the form 0f a relativelythin 'fan shaped sheet. The surface of the arc may also be increased byoperating under reduced pressure as hereinafter described.

The main body of oil in the reaction vessel may be heated to any desiredtemperature by passage of electric current through heatingrcoil 40, orby applying heat to such oil in any` other suitable manner. Thetemperature to which such body of oil is heated is indicated bythermometer 45, and is preferably Leraars the highest temperaturetolwhich the oil may be heated at the pressure prevailing in thereaction chamber, without causing appreciable vaporization thereof. Thistemperature, while it may in some cases be considerably aboveatmospheric temperature, is yet suliiciently below the high temperatureof the dissociation zoneto provide the above= described cooling effecton the carbon black disseminated therein from the dissociation zone.

I will now describe the complete process of producing printing inkaccording to my invention, in the case in which a sub-atmosphericpressure or vacuum is maintained within the system, using the apparatusshown in Fig. 1. The oil to be used in the process is supplied to supplychamber 1 throu h pipe 5. Such oil may be any hydrocar on or othercarbon-bearing oil which is suitable for use as a vehicle for printingink, which is sufficiently Huid for passage through the various parts ofthe apparatus, and which is susceptible to dissociation at` hightemperature to form carbon asa product of such dissociation. Byoperation of exhaust fan or vacuum pump 16', a suitable vacuum orsubatmospheric pressure is maintained Within the apparatus and theconnection of equalizing pipes 23, 24 and 25 insures that such vacuumwill be substantially uniform in the different parts of the apparatus.'A. suiiicient quantity of oil is then passed from supply chamber 1 intoreaction vessel 3 to pro# vide the aforesaid body of oil in said reac.tion vessel. Such body of oil may then be heated by heating coil 4:0 toa suitable temperature say from 200 to 1200o F., and the arc is thenestablished between the rotating electrodes 16 as above described. Thehydrogen and other gases produced by the resulting dissociation of oilat the surfaces of the arc passes upwardly through the body of oilintothe space through pipe 12 to scrubber 2, where it encounters thedescending stream of oil in such scrubber. Any condensible constituentscarried off with such gaseous products are thus condensed and absorbedin the oil and are returned to reaction vessel 3, While the gasesthemselves are discharged through pipe 17 The carbon black formed at thesurface of the dissociation zone, and immediately thereafterdisseminated into the body of relatively cool oil, the oil in a veryfinely divided state and as such oil is repeatedly circulated throughthe dissociation zone the proportion of carbon black in suspensiontherein gradually increases and this process may be` carried out until asufficient 'quantity of the oil has been dissociated to providethroughout the body of oil in the reaction vessel the proportions ofcarbon black required in printing ink, so that the entire charge of oilhas been con- 38 and hence out ksure is remains in suspensionin/in'gfpipes 23, and 25.

verted to printing ink. In general, however, I prefer to provide forslow but continual and slow but continual withdrawal of printing inkfrom the reaction vessel through pipe 18 into storage chamber el. Sincepipe 18 leads from the bottom of the reaction vessel it will be seenthat the thickest portion of the charge in the reaction vessel, that isthe portion containing the highest proportion of carbon black, iscontinually withdrawn therefrom. It is possible therefore by a properregulation of valves 9 and 19 to maintain the rate of flow of oil intothe top of the reaction vessel and of ink out of the bottom of suchvessel such that the ink discharged therefrom contains a uniform andsuitable proportion of carbon black. The storage chamber 4 is in thiscase provided chiefly for the purpose of permitting further mixing ofthel material discharged from the reaction vessel so as to correct anyminor or momentary fluctuations or inequalities in the compositionthereof. The mixed ink containing substantially the necessary pro-.portion of carbon black finally passes through pipe 21 to any suitablepoint for further treatment, storage or shipment.

The vacuum which ismaintained in the system will in general depend uponthe volatility of the oil employed in the process and may vary, forexample, from l of an at'- mosphere absolute pressure in the case of aheavy or diificultly volatile oil to but slightly under atmosphericpressure in the case of a light or readily volatile oil. In some casesthe process may be carried out 'entirely at atmospheric pressure as, forexamp1e,when Working with an oil of such volatility that the use ofreduced pressure would result in undue vaporization thereof at thetemperaure of the body of oil in the reaction cham- The process may alsobe carried out under super-atmospheric pressure using, for example, theapparatus shown in Fig. 2. The operations are in this case substantiallythe same as above described with the exception that valve 14 is soregulated as to cause the gaseous `products formed by the dissociationof the oil-to.-createthe desired super-atmospheric pressure in thesystem and such presas before maintained uniform by means of equaliz- Inthis case a suiiicient charge of oil may be supplied to oil supplychamber 1 to last for a complete run ofthe process which is then carriedout as a batch process, or the oil may be continually supplied to suchsupply chamber through pipe 5 under a pressure suliciently greater thanthat maintained within the system to cause the desiredllow of oil. Bymeans of pre-heater 28 the oil passing-from scrubber 2 to reactionchamber 3 may be heated subthroughout the system feeding of oil to thereaction vessel is provided as before withA pipes 12 (or 29) 18 forsupplying oil thereto and for conducting ink therefrom land may also beprovided with heating coil 40. In this case, however, I have shown therotating electrodes 46 as mounted with their axes vertical. The shaft 67of one of said electrodes passes through stuiing box 68 and is providedat its outer end with a bevel gear 69 engaging bevel gear 70 on theshaft of motor 71 in such manner that rotation of said motor causes thecorresponding electrode to be rotated at high velocity. The shaft 72 ofthe other electrode passes through'an insulating bushing 73 and stuffingbox 74 and is provided at its outer end with a contact ring 75. Acontact brush 76 engages said contact ring and is connected by wire 77to one side .f of the secondary winding of transformer 60,

the other side of said winding being connected by wire 78 to themetallic wall of vessel 36 and hence through shaft 67 to the electrode46 on said shaft. The insulating bushin 73 may be mounted on a slidincover p ate 79 so' as to permit the-correspon ing electrode to be movedtoward or away from the other electrode and vary the gap between suchelectrodes.

. The operation of this form of reaction vessel is substantially thesame as above described with the chief exception that only the electrodeon shaft 67 is positively rotated, the other electrode being rotatedonlyl by the action of friction between the opposing surfaces of theelectrodes and the ody of oil therebetween.y At the high velocityemployed, such friction is sufficient to effectively impart rotativemovement to said other electrode so as to produce as before a spreadingof the arc for the purposes above described.

In the form of reaction vessel shown in Figs.'8 and 9 only onerotatingelectrode 81 is provided, said electrode having' a rounded rojecting end82 and being mounted at the ower end of shaft 83 which passes throughinsulating bushing 84 and is driven by means of belt 85 engaging pulley86 on said shaft. The other electrode comprises a ixed ring 87surrounding electrode 81 in such manner that rotation of electrode 81causes the rojecting end A82 thereof to rotate at a ed distance from theinner surface ofcontact can no longer be maintained, when such arc isbroken and a new arc established in the Vsame manner. A continual seriesof arcs are thus produced following one another 1n such rapid successionas to give substantially the effect of a continuous arc in the annularspace between electrode 87 and the path of v the projecting end ofelectrode 81. Theoil is as before continually drawn into and throughthis arc or dissociation zone,'and

I prefer as shown to incline or taper the inner surface of electrode 87and the end of electrode 81 inwardly toward the bottom of the reactionvessel so that the whirling movement imparted to. the oil by rotation ofelectrode 81 also serves to draw the oil upwardlythrough the aforesaiddissociation zone. It' desired, the electrode 81 may be provided withadditional projections as at 82.

In Figs. 10 and 11 I have shown a reaction vessel provided with meansfor maintaining a high temperature dissociation zone by means of anOxy-hydrogen flame or other high temperature fiame. In this case anouter tube 90 and an inner tube 91 Within said outer tube extendupwardly throuuh the top of vessel 36 and are adapted to e rotated athigh velocity by means of motor 92,'belt 93 and pulley 94. Tube 90 opensat its upper end into chamber to whichl oxygen or compressed air issupplied through pipe 96, while pipe 91 opens into chamber 97 to whichhydrogen or other combustible gas is supplied through pipe 98.

Tubes 90 and 91 are provided as shown with 4 horizont-al extensions attheir lower ends which project radially inthe vessel 36 and a burnerhead 99 is provided at the outer end ofthe radially projectlng portionsof said pipes. Said burner head is provided `with passages 101 and 102communicating respectively with tubes 90 and 91 and terminating 1nburner tips 103 and 104 for supplying oxygen and hydrogen respectivelyinto intimate contact with one another. Means are preferably providedfor igniting the'resulting mixture of oxygen and hydrogen beneath thesurface of the body of4 oil, such means comprising, for example, a pairof spark points 105 and 106. One of these points 105 may be grounded asthrough the walls of vessel 36, and the other may be connected as shownby an insulated wire 107 v-/hyd'rogem sociation vof the oil also burnsin the flame,

' ing substantially the same as descri if tween points 105 and 106. Thepipes and burner are set in rotation at suitable velocity, so that thedissociation zone of high temperature is caused to move through the oilwhich as before is dissociated at the surfaces of this Zone to formcarbon black and The hydrogen produced by disand the combustion productspass od through pipe 12.

Any of the above described reaction vessels may be utilized as thereaction vessel 3 in the apparatus shown in Figs. land 2, the operationof the complete apparlats be- In some cases it may be found desirable toprovide for more positive circulation of the oil through thedissociation zone and for more prolonged settling of the carbon fromthe` oil between successive passages therethrough. Furthermore in somecases it may be impracticable to produce by .direct dissociation in thereaction chamber a sufficiently high concentration of carbon black inthe oil. I may therefore provide in such cases for removing oil withcarbon black in suspension therein from the reaction chamber, subjectingsuch oil to a settling operation outside the reaction chamber to obtaina settled or thickened portion 'having substantially the composition ofprinting ink and a supernatant portion containing a relatively lowproportion of carbon black and returning such oil containing arelatively low proportion of carbon black to the reaction chamber fordissociation of a further portion thereof.

The apparatus shown in Fig. 12 may be used for carrying out the processin this manner. Such apparatus is substantially the same as that shownin Fig. 2 except that a settling chamber 112 is substituted for storagechamber 4, and pump 113 and pipe 114 controlled by valve 115 areprovided for returning supernatant oil containing a relatively smallproportion of carbon black to the oil supply chamber 1 where itismixed'with the incoming oil supplied through pipe 5 and is returned tothe reaction chamber for further dissociation. Settling chamber 112maybe providedwith outletl pipe 116 ycontrolled by valve 117, forremoval of the finished link therefrom. In carrying out the process inthis manner the rate of flow of the oil is so regulated by operation ofvalves'9,

35, 19, 115, and 117 that a continual supply' chamber 3 to settlingchamber 112 does not contain sulficient carbon black to permit its.

use as ink, but the period of settling in said settling vchamber issullicient to provide a settled portion which does contain suchnecessary proportion of carbon black, while the upper or supernatantportion of the oil containing a relatively small proportion of carbonblack is continually drawn off and returned by pump 118 to supplychamber 1.-y

Another modification of the process which is of advantage, when the oilto be used as a vehicle for the ink is so heavy as to interfere with theflow thereof through the several parts of the apparatus and the rapidcirculation thereof in the reaction chamber, consists in mixing withthis heavy oil a relatively light oil so as to increase the .fluiditythereof, subjecting the mixture to thermal dissociation in the mannerabove' described so' as decompose portions of both the heavy and lightconstituents of the mixture to form carbon black and thereaftersubjecting the mixture with the carbon black in suspension therein to adistilling operation to remove the remaining lighter oil therefrom andreturning snch lighter oil for mixture with a further quantity of heavyoil for use in the process. This method of operation may be carried outin the apparatus shown in Fig. 13 which is substantially the same asthat shown in Fig. 12 but comprises in addition a still 119 of anysuitable type, a pipe 120 con-l trolled by valve 121 for 'conductingsettled material from settling chamber 112 to said still, a condenser122, a for conducting vapor from said still to said condenser, and apump 124 and pipe 125 `for returning condensed light oil from saidcondenser to tank 1 which in this case is adapted to serve both as amixing and storage tank. Two'feed lines 126 and 127 controlledrespectively by valves 128 and 129 are provided for supplying to tank 1the heavy oil which is to form the vehicle in the finished ink and thelight oil for dilution thereof, Suitable agitating means 128 may beprovided in tanltl. i

In carryingout this modification of the process the heavy oil and lightoil are'introf duced to tank 1 through pipes 126 and 127 respectively insuch proportionsas to produce a mixture of the desired fluidity, forexample,.a mixture containing equal parts of heavy and light oil,allowance being made, however, for the light oil returning through pipe123' pipe 125 and also for the amount and composition oflsupernatant oilreturned through pipe 114. The oil is thoroughly mixed in tank 1 and theresulting mixture is subjected to any of the above described operationsfor effectmg thermal dissociation of the oil and producing a suspensionof carbon black in the oil, includingr if desired a settling operationin chamber 112 and the return of the less concentrated portion throughpipe 114 to tank 1. The suspension of carbon black in the oil, or thesettled portion thereof if a settling operation be employed, passesthrough pipe 120 to still 119, wherein it is heated to a sufficienttemperature and for a suflicient length of time to vaporizesubstantially all`of t-he remaining light oil, which is collected incondenser 122 and returned through pipe 125 to tank 1, while the heavyoil containing substantially the necessary proportion of carbon blackfor use as printing ink is drawn oit' continually' or intermittentlyfrom the still through pipe 118.

Another arrangement of apparatus .suitable for carrying out my inventionis illustrated diagrammatically in Fig. 14. A series of reaction vessels3, 3 and 3" are provided, Which are connected by pipes 18 to centrifugalseparators 132, 133, and 134 respectively. Pipe 29 leads-from scrubber 2to the first vessel 3 for supplying thereto the oil to be treated. Eachof the separators is provided'with two discharge pipes 135 and 136, forthe lighter and heavier fr actions, containing respectively low and highpercentages of carbon black. The lighter material from se arator 132 ispassed by pump 137 and plpe 138 to the second reaction vessel 3, Whilethe lighter fractions from the separators 133 and 134 are passed, bypumps 139 and 140 and pipes 141 and 142 respectively, to the thirdreaction vessel 3. The heavier fractions from all the separators arepassed through pumps 143 and pipes 144 to storage chamber 145. Saidstorage chamber may be adapted to serve as a.settlin g chamber orseparator for removal vof any heavy particles such as grit, and a drainpipe 146 `controlled by valve 147 may be provided at the bottom of saidchamber, through which such heavymaterial may be withdrawn from time totime. Pipe 148 controlled by valve 149- leads from somewhat above thebottom of chamberl 145 to al pair of rotating milling rolls 150 forbreaking up any large lumpsvof carbon black so as to produce 'a smoothink. The material passing through the rolls collects in tank 151 andis-condicted through pipe 152 to any suitable point for storage or anyother purpose. Pipes 153 conduct the hydrogen and otherv gases from thereaction vessels to scrubber 2.

In carrying out the process in this apparatus the oil passes first tovessel 3 wherein is `formed. The material fromV this reaction vessel isagain separated in separator 133,

the heavier portion passing as before to chamber 145 and the lighterportion to the next reaction vessel 3". The process is again repeated,with the exception that the lighter portion from separator 134 isreturned to the same reaction vessel 3 for further treatment. The oilpassing to chamber 145 therefore contains the proportion of carbon blackrequired for ink. Any heavy particles, such as pieces. of carbon fromthe eleeetrodes, grit, or other foreign matter, is permitted to settleto the bottom of chamber 145, While the finished ink, free from suchforeign substances, passes to the milling rolls 150 in which any lumpsof carbon black are broken up and a smooth ink of uniform consistency isproduced.

The main distinctions between this modification of the invention and theothers above described are that the oil passes successively through `aseries of dissociation zones or reaction vessels, with a separation of amore concentrated portion thereof between successive passages, insteadofrepeatedly passing through the same dissociation zone or reactionvessel, and that the separation of the more concentrated portion iseffected by means of a centrifugin operation rather than by gravitativesett ing. Such centrifuging operation has the advanta es of more perfectand rapid separationan conservation of space required and in some casesmay be preferable to the use of settlin tanks.

It will of course be understoo that the centrifu al separating meansshown in Fig.

may be used inconjunction with any of the other forms of apparatus. Forexample, as

lill) indicated in dotted lines in Fig. 13, the dis- 'charge pipe 118may, if desired, lead to a settling chamber 145, provided with an outletpi e 146 at the bottom for Lremoval of sett e side for removal of inkfreed from such material; and a. pair of milling rolls 15() may be heavymaterial and a pipe 148 in itsA provided for treating the ink drawn othrough pipe 148 so as to break up any lumps of carbon black in the ink.

For some purposes the material produced by any of the methods abovedescribed may be used directly as printing ink, while for other purposesit may be necessary to add certain other ingredients, such as highergrade oils, dryers, varnishes, or the like in order to obtain an ink ofthe desired grade. Such other ingi'edients may be added in any suitablemanner; for example, as shown in Figs. 13 and 14, such an ingredient maybe placed in tank 155 and may be supplied through pipe 156 to themilling rolls 150 along with material supplied through pipe 148, so asto be mixed therewith during the milling operation. Y

It will be, of course, understood that in any of the processes abovedescribed the exact composition of the final product may vary somewhat,from time to time, above or below the required composition of printingink, but such minor fluctuations are compensated for by mixing obtainedin the storage tank 4 or in other storage or mixing means into which theink may be conducted for this purpose.

I claim:

1. The process of making printing ink which comprises subjecting acarbon-bearing oil suitable for use as a vehiclejin printing ink to ahigh temperature in a localized zone to effect dissociation of a portionthereof into carbon black and gaseous products, causing' the carbon soproduced to be immediately -removed from said zone vand disseminatedinto the undissociated oil surrounding said zone, continuing suchtreatment until a portion at least of such oil contains a sufficientproportion of carbon black for use as printing ink, and removing the oilcontaining such proportion of carbon black.

2. The process of making a printing ink which comprises maintaining abody of carbon-bearing oil suitable for use as a vehicle for printingink, establishing a localized zone of high temperature Within said bodyof oil, causing such oil to circulate in such manner as to continuallybring fresh portions thereof into contact With such .high temperaturezone to cause dissociation thereof into carbon black and gaseousproducts and to continually remove v*such carbon black and gaseousproducts of dissociation fromsaid zone into said body of oilsubstantially immediately aft-er their formation, removing the `gaseousproducts from the oil, continuing such treatment until at least aportion of the oil vcontains a suicient proportion of carbon black foruse as printing ink, and

removing from the process oil containing i suchproportion of carbonblack.

3. A process as setforth in claim Q heat being also supplied to 'saidbody of oil outwhich comprises subjecting a carbon-bearing oil suitablefor use as a vehicle in printing ink to a high temperature to effectdissociation of a portion thereof into carbon black and gaseousproducts, causing the carbon black so produced to be disseminated intothe undissociated oil, subjecting oil containing such carbon black sodisseminated therein to a settling operation, separating a settledportion of such oil containing substantially theproportion of carbonblack required for use as 'printing ink and return'- ing the remainderof such oil containing a relatively small proportion of carbon blackl tofurther high temperature dissociation for the formation of au additionalquantity of carbon black.

5. 'llie process of making printingink` which comprises forming amixture of a relatively heavy carbon-bearing oil suitable .i

for use as a vehicle in printing ink and a relatively lightcarbon-bearing oil, subjecting such mixture to a high temperature toeffect dissociation of portions thereof into carbon black and gaseousproducts, causing the carbon black so produced to be dissemi"L natedinto the undissociated mixture, subjccting such mixture containing suchcarbon black so disseminated therein to a distilllng operation tovaporize undissociated relativev ly light oil therefrom and leave asuspension of carbon black in relatively heavy ies condensing thevaporized lighteroil and rei turning the condensed light oil for mixtureWith a further quantity of relatively heavy oil for use in the aboveprocess.

6. The method of producing carbonl black in suspension in oil whichcomprises main-- taining a body of carbon-bearing oil, establishing alocalized zone of high temperature Within said body of oil, 'causingsuch oil to circulate in such manner as to continually bring freshportions thereof into contact with suc-h high temperature zone to causedissociation thereof to form carbon black andl gaseous products and tocontinually i'emove such carbon black and *gaseous` products ofdissociation from said zone into said body of oil, and'removing thegaseous prod ucts from the oil, While supplying 'heat to said body ofoil in addition to heat received thereby from said high temperature zonein sufficient amountv to maintain such body of oil at a temperaturematerially above atmospheric temperaturebut suiiiciently below thetemperature ci said. high temperature zone to prevent harmful changes inthe properties of the carbon black after dissemination in said body ofoil.

7'. A process as set forth in claim 6, said body of oil being maintainedunder a pressure only slightly in excess of the vapor pressure of themost volatile constituent of the oil at the temperature at which saidbody ,of oil is maintained.

8. A process as set forth in claim 6, said body of oil being maintainedunder a pressure below atmospheric pressure but slightly in excess ofthe Vapor pressure of the most volatile constituent of the oil at thetemperature at which the body of oil is maintained.

9. The process of forming carbon black in suspension in oil whichcomprises maintaining a body of carbon-bearing oil, establishing alocalized zone of high temperature within said body of oil, causing suchoil to circulate so as to bring portions thereof into contact with suchhigh temperature zone to cause dissociation thereof into carbon .blackand gaseous products and to continually remove such carbon black andgaseous products of dissociation from said zone into said body of oil,and removing the gaseous products from the oil, while maintaining saidbody of oil under a pressure only slightly greater thanthe vaporpressure of the most volatile constituent of the oil at the temperatureat which such body of oil outside said. high temperature zone ismaintained.

10. A process as set forth in claim 9, said pressure being belowatmospheric pressure.

11. An' apparatus for producing a suspension of carbon black in an oil,comprising a reaction chamber adapted to contain a. body of oil, meansfor supplying oil to such reaction chamber, means in said chamber andbeneath the surface of the body of oil therein for maintaining alocalized zone of high temperature within said body of oil, ad ditionalmeans for supplying heat to said body of oil in the reaction chamber,but outside said high temperature zone to heat the same to a temperatureabove atmospheric but below the temperature of such high temperaturezone, and outlet means at the lower portion of said reaction chamber,said reaction chamber being of sutlicient size relative to the size ofsaid high temperature zone to permit repeated circulation of the oiltherein through said high temperature zone.

12. An apparatus for producing carbon black comprising a reactionchamber adapted to contain a body of oil, means for mixing a relativelyheavy oil and a relatively light oil, means for supplying such mixtureto said reaction chamber to maintain said body of oil therein, means formaintaining a localized zone of high temperature within said body of oilto produce carbon black in suspension in such oil, means for withdrawingmaterial from the lower portion of said reaction cha-mber, means forsubjecting material so withdrawn to a distilling operation to vaporizeconstituents of said relatively light oil, means for fcondensing suchvaporized constituents, and means for supplying such condensed materialtogether with said mixture of relatively light and relatively heavy oilto said reaction chamber.

13. The process of making printing ink, which comprises subjecting acarbon-bearing oil suitable for use as a vehicle in printing ink to ahigh temperature to effect dissocia-v tion of al portion thereof intocarbon black 'and gaseous products, causing the carbon black so producedto be disseminated into the oil, subjecting oil containing such carbonblack so disseminated therein to a separating operation to separate thesame into a portion containing substantially the requisite proportion ofcarbon black for printing ink and a portion containing a smallerproportion of carbon black, and subjecting the latter portion tofurtherhigh temperature dissociation for the formation of additionalcarbon black. y

In testimony whereof I have hereunto subscribed my name this 25th day ofOctober,

JOHN J. JAKOSKY.

